CN107252680B - Preparation method of biological membrane carrier - Google Patents

Preparation method of biological membrane carrier Download PDF

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CN107252680B
CN107252680B CN201710424414.0A CN201710424414A CN107252680B CN 107252680 B CN107252680 B CN 107252680B CN 201710424414 A CN201710424414 A CN 201710424414A CN 107252680 B CN107252680 B CN 107252680B
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carrier
solution
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mass ratio
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CN107252680A (en
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李小兰
林晨
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Shenmei Technology Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4868—Cells, spores, bacteria
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention relates to a preparation method of a biomembrane carrier, belonging to the technical field of water treatment. The invention takes diatomite as a template, a layer of chelating film layer is formed on the surface of the template through dopamine to adsorb calcium ions, then phosphorus pentoxide and alcohol are generated through combustion of white phosphorus to react to generate phospholipid, the phospholipid is hydrolyzed under the action of ammonia water, hydroxyl on a hydrolysate is slowly combined with calcium ions to generate crystal nucleus and grow gradually, and finally a carrier crude product with calcium hydroxy phosphate on the surface is obtained, while the biocompatibility of the calcium hydroxy phosphate is good, thereby solving the problem of poor biocompatibility of the traditional biomembrane carrier and the microorganism, saponin and organic carboxylic acid in the biological fermentation liquid increase the number of hydrophilic groups on the surface of the carrier under the action of the microorganism, improve the surface wettability of the carrier, increase the contact probability of sewage and the carrier, provide more attachment sites while providing nutrient sources, reduce the attachment difficulty of the microorganism and shorten the film hanging time, has wide application prospect.

Description

Preparation method of biological membrane carrier
Technical Field
The invention relates to a preparation method of a biomembrane carrier, belonging to the technical field of water treatment.
Background
The biomembrane process is a waste water treatment method for oxidizing and degrading organic matters in waste water by utilizing microorganisms attached to and growing on the surfaces of certain solids, namely microbial membranes through solid-liquid phase substance conversion. In recent years, the biofilm method has been widely applied to sewage/wastewater treatment with the advantages of high treatment efficiency, strong impact load resistance, stable operation, small sludge yield, economy, energy conservation and the like. The common biomembrane reactor mainly comprises a biological filter, a biological rotating disk, a biological contact oxidation tank, a biological fluidized bed and the like. Biofilms are ecosystems composed of highly dense aerobic bacteria, anaerobic bacteria, facultative bacteria, fungi, protozoa, and algae, with solid media called filter materials or carriers attached. The carrier is the core part of the biofilm method, plays an important role in aerobic, facultative and anaerobic processes, and the treatment effect of the process is directly influenced by the material quality, the specific surface area, the water and gas distribution performance, the surface roughness, the strength, the density and other factors of the carrier. The conventional biofilm carriers are mainly classified into inorganic, organic synthetic and natural degradable polymers according to materials. However, the compatibility of the conventional biofilm carrier with microorganisms is poor, so that the microbial attachment difficulty is high, the biofilm formation time is long, the carrier hydrophilicity is poor, the surface is difficult to wet, and the use effect of the biofilm is influenced.
Therefore, the invention discloses a novel biomembrane carrier with strong compatibility with microorganisms and good surface wettability, and has positive significance for the technical field of water treatment.
Disclosure of Invention
The invention aims to solve the technical problems that the existing common biomembrane carrier has poor compatibility with microorganisms, so that the microorganism has high attachment difficulty, long membrane hanging time, poor carrier hydrophilicity and difficult surface wetting, and the using effect of the biomembrane is influenced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
(1) spraying and freezing kieselguhr with liquid nitrogen for 2-3 min, mashing the frozen kieselguhr, drying, crushing again, screening out kieselguhr particles with the particle size of 1-3 mm, mixing the kieselguhr particles with a dopamine solution to prepare a mixed solution, adjusting the pH of the mixed solution to 8.0-8.2 with a sodium hydroxide solution, performing ultrasonic oscillation treatment on the mixed solution after the pH is adjusted, standing for aging, and filtering and separating to obtain filter residues for later use;
(2) igniting white phosphorus to burn, collecting a burned product, mixing and stirring the burned product and absolute ethyl alcohol according to a mass ratio of 1:10 for 2-3 hours to obtain a reaction solution for later use;
(3) dissolving calcium nitrate into deionized water according to the mass ratio of 1:10 to obtain a calcium nitrate solution, pouring the filter residue for use in the step (1) into the calcium nitrate solution according to the mass ratio of 1:5, and placing the calcium nitrate solution into a high-shear emulsifying and dispersing instrument for dispersing for 15-20 min to obtain a dispersion liquid;
(4) filling the dispersion into a three-neck flask, transferring the three-neck flask into a water bath kettle, dropwise adding ammonia water with the mass fraction of 25% into the three-neck flask, and adjusting the pH value of the dispersion to 9.5-10.0;
(5) after the pH is adjusted, stirring by using a stirrer, dripping the reaction liquid prepared in the step (2) into a three-neck flask in the stirring process, controlling the dripping speed to be 10-15 mL/min, and after the dripping of the reaction liquid is finished, continuing stirring and reacting for 20-30 min;
(6) after the stirring reaction is finished, transferring the three-neck flask into a sand bath, standing and aging for 10-12 h, filtering, separating to obtain a filter cake, washing for 10-15 min by using absolute ethyl alcohol and deionized water in sequence, and drying to obtain a crude carrier product;
(7) weighing 3-5 kg of saponaria pods and 1-2 kg of grapes, mixing and crushing to obtain mixed slurry, mixing the mixed slurry and water according to an equal mass ratio, loading the mixture into a fermentation tank, carrying out heat preservation fermentation, filtering and separating after the fermentation is finished to obtain fermentation liquor, mixing the carrier crude product and the fermentation liquor, placing the mixture in a greenhouse, naturally standing for reaction, filtering and separating after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a modified carrier crude product for later use;
(8) mixing peach gum, honey, agar and water, putting the mixture into a beaker, transferring the beaker into an oil bath pot, stirring and mixing to obtain a mixed solution, and concentrating the mixed solution to 1/3 of the volume of the mixed solution to obtain a concentrated solution;
(9) and (4) immersing the crude modified carrier prepared in the step (7) into the concentrated solution, carrying out ultrasonic oscillation treatment, filtering, separating to obtain immersion filter residues, carrying out freeze drying on the immersion filter residues, and discharging to obtain the biomembrane carrier.
The mass ratio of the diatomite particles to the dopamine solution in the step (1) is 1:5, the mass concentration of the dopamine solution is 4g/L, the concentration of the sodium hydroxide solution is 0.5mol/L, the ultrasonic oscillation frequency is 40-50 kHz, the ultrasonic oscillation time is 20-30 min, and the standing and aging time is 1-2 h.
The temperature of the water bath kettle is 60-70 ℃.
The temperature of the sand bath pot is 170-180 ℃.
The heat preservation fermentation temperature in the step (7) is 22-25 ℃, the heat preservation fermentation time is 15-20 days, the mass ratio of the carrier crude product to the fermentation liquid is 1:3, the temperature of a greenhouse is 30-40 ℃, the relative humidity of air is 60-70%, and the standing reaction time is 20-24 hours.
The mass ratio of the peach gum, the honey, the agar and the water in the step (8) is 20:5:2:40, and the temperature of the oil bath pot is 80-90 ℃.
The ultrasonic oscillation frequency in the step (9) is 40-50 kHz, the ultrasonic oscillation time is 20-30 min, the freeze drying temperature is-30 to-20 ℃, and the freeze drying time is 1-2 h.
The invention has the beneficial effects that:
(1) according to the method, firstly, diatomite with huge porosity and specific surface area is used as a template, self-polymerization crosslinking reaction is carried out on the surface of the template through dopamine, a film layer with initial chelation is formed, the film layer is chelated and adsorbs calcium ions in calcium nitrate and is uniformly distributed on the surface of the template, then phosphorus pentoxide is generated through white phosphorus combustion, the phosphorus pentoxide reacts with alcohol to generate phospholipid, the phospholipid is gradually hydrolyzed under the action of ammonia water, hydroxyl on a phospholipid hydrolysis product is slowly combined with the calcium ions on the surface of the template to generate crystal nuclei, and the crystal nuclei grow gradually along with the increase of time, so that a carrier crude product with calcium hydroxy phosphate on the surface is finally obtained, the biocompatibility of the calcium hydroxy phosphate is good, and the problem of poor compatibility between the traditional biological film carrier and microorganisms is solved;
(2) the biological fermentation liquor used by the invention contains abundant saponin and organic carboxylic acid, the surface of the carrier can be modified under the action of microorganisms, the number of hydrophilic groups on the surface of the carrier is increased, the saponin can improve the surface wettability of the carrier and increase the contact probability of sewage and the carrier, the load of nutrient substances can provide a nutrient source and more attachment sites for the microorganisms, the attachment difficulty of the microorganisms is greatly reduced, the membrane hanging time of the microorganisms is shortened, and the biological fermentation liquor has a wide application prospect.
Detailed Description
Weighing 4-5 kg of diatomite, spraying and freezing the diatomite for 2-3 min by using liquid nitrogen, transferring the frozen diatomite into a stone mortar, mashing the diatomite for 1-2 h by using a stone pestle, putting the mashed diatomite into an oven, drying the diatomite for 30-40 min at 105-110 ℃, transferring the diatomite into a crusher after drying, continuously crushing the diatomite for 20-30 min, and screening out diatomite particles with the particle size of 1-3 mm; mixing diatomite particles and a dopamine solution with the mass concentration of 4g/L according to the mass ratio of 1:5 to prepare a mixed solution, adjusting the pH value of the mixed solution to 8.0-8.2 by using a sodium hydroxide solution with the concentration of 0.5mol/L, transferring the mixed solution into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment at the frequency of 40-50 kHz for 20-30 min, standing and aging for 1-2 h, and filtering and separating to obtain filter residues; weighing 10-20 g of white phosphorus, igniting the white phosphorus to burn, collecting a burned product, mixing the burned product with absolute ethyl alcohol according to the mass ratio of 1:10, and stirring and mixing the mixture for 2-3 hours by using a magnetic stirrer at the rotating speed of 200-300 r/min to obtain a reaction solution; weighing 15-30 g of calcium nitrate, dissolving in 150-300 mL of deionized water to obtain a calcium nitrate solution, pouring the filter residue into the calcium nitrate solution according to the mass ratio of 1:5, and dispersing in a high-shear emulsification disperser for 15-20 min to obtain a dispersion liquid; transferring the dispersion liquid into a three-neck flask with a dropping funnel and a stirring device, transferring the three-neck flask into a water bath kettle, raising the temperature of the water bath kettle to 60-70 ℃, firstly dropwise adding 25% ammonia water by mass into the three-neck flask through the dropping funnel, and adjusting the pH value of the dispersion liquid to 9.5-10.0; after the pH is adjusted, starting a stirrer to stir at a rotating speed of 200-300 r/min, dripping the reaction liquid into a three-neck flask through a dropping funnel in the stirring process, controlling the dripping speed to be 10-15 mL/min, and after the dripping of the reaction liquid is finished, continuing stirring and reacting for 20-30 min; after the stirring reaction is finished, transferring the three-neck flask into a sand bath kettle, increasing the sand bath temperature to 170-180 ℃, standing and aging for 10-12 h, filtering, separating to obtain a filter cake, sequentially washing with absolute ethyl alcohol and deionized water for 10-15 min, putting into an oven, and drying at 105-110 ℃ for 1-2 h to obtain a crude carrier product; weighing 3-5 kg of saponaria pods and 1-2 kg of grapes, putting the saponaria pods and the grapes into a grinder, grinding for 20-30 min to obtain mixed slurry, mixing the mixed slurry and water according to an equal mass ratio, putting the mixture into a fermentation tank, sealing the opening of the fermentation tank, performing heat preservation fermentation at 22-25 ℃ for 15-20 days, and filtering and separating to obtain fermentation liquor after the fermentation is finished; mixing the crude carrier product with fermentation liquor according to the mass ratio of 1:3, placing the mixture in a greenhouse at the temperature of 30-40 ℃ and the relative air humidity of 60-70%, naturally standing for reaction for 20-24 hours, filtering and separating after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a crude modified carrier product; mixing peach gum, honey, agar and water according to a mass ratio of 20:5:2:40, then putting the mixture into a beaker, then transferring the beaker into an oil bath pot, heating to 80-90 ℃, stirring and mixing for 10-15 min to obtain a mixed solution, then transferring the mixed solution into a rotary evaporator, and carrying out rotary evaporation and concentration to 1/3 of the original volume of the mixed solution to obtain a concentrated solution; and (2) immersing the crude modified carrier into the concentrated solution according to the mass ratio of 1:10, putting the crude modified carrier into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment for 20-30 min at the frequency of 40-50 kHz, filtering, separating to obtain impregnated filter residues, putting the impregnated filter residues into a freeze dryer, drying for 1-2 h at the temperature of-30-20 ℃, and discharging to obtain the biomembrane carrier.
Example 1
Weighing 5kg of diatomite, spraying and freezing the diatomite for 3min by using liquid nitrogen, transferring the frozen diatomite into a stone mortar, mashing the diatomite for 2h by using a stone pestle, putting the mashed diatomite into an oven, drying the diatomite at 110 ℃ for 40min, transferring the diatomite into a grinder after drying, continuously grinding the diatomite for 30min, and screening out diatomite particles with the particle size of 3 mm; mixing diatomite particles and a dopamine solution with the mass concentration of 4g/L according to the mass ratio of 1:5 to prepare a mixed solution, adjusting the pH value of the mixed solution to 8.2 by using a sodium hydroxide solution with the concentration of 0.5mol/L, transferring the mixed solution into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment for 30min at the frequency of 50kHz, standing and aging for 2h, and filtering and separating to obtain filter residues; weighing 20g of white phosphorus, igniting the white phosphorus to burn, collecting a burned product, mixing the burned product with absolute ethyl alcohol according to the mass ratio of 1:10, and stirring and mixing the mixture for 3 hours at the rotating speed of 300r/min by using a magnetic stirrer to obtain a reaction solution; weighing 30g of calcium nitrate, dissolving in 300mL of deionized water to obtain a calcium nitrate solution, pouring the filter residue into the calcium nitrate solution according to the mass ratio of 1:5, and dispersing in a high-shear emulsifying and dispersing instrument for 20min to obtain a dispersion liquid; transferring the dispersion liquid into a three-neck flask with a dropping funnel and a stirring device, transferring the three-neck flask into a water bath kettle, raising the temperature of the water bath kettle to 70 ℃, firstly dropwise adding ammonia water with the mass fraction of 25% into the three-neck flask through the dropping funnel, and adjusting the pH value of the dispersion liquid to 9.7; after the pH is adjusted, starting a stirrer to stir at a rotating speed of 250r/min, dripping the reaction liquid into a three-neck flask through a dropping funnel in the stirring process, controlling the dripping speed to be 15mL/min, and after the dripping of the reaction liquid is finished, continuing stirring and reacting for 30 min; after the stirring reaction is finished, transferring the three-neck flask into a sand bath kettle, increasing the sand bath temperature to 180 ℃, standing and aging for 12 hours, filtering, separating to obtain a filter cake, sequentially washing with absolute ethyl alcohol and deionized water for 15 minutes, putting into an oven, and drying at 110 ℃ for 2 hours to obtain a crude carrier; weighing 5kg of saponaria mollissima and 2kg of grapes, putting the saponaria mollissima and the grapes into a grinder, grinding for 30min to obtain mixed slurry, mixing the mixed slurry and water according to equal mass ratio, putting the mixture into a fermentation tank, sealing the opening of the fermentation tank, performing heat preservation fermentation at 25 ℃ for 20 days, and filtering and separating to obtain fermentation liquor after the fermentation is finished; mixing the crude carrier product with fermentation liquor according to the mass ratio of 1:3, placing the mixture in a greenhouse at the temperature of 40 ℃ and the relative air humidity of 70%, naturally standing for 24 hours for reaction, filtering and separating the mixture after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a crude modified carrier product; mixing peach gum, honey, agar and water according to the mass ratio of 20:5:2:40, then putting the mixture into a beaker, then transferring the beaker into an oil bath pot, heating to 90 ℃, stirring and mixing for 15min to obtain a mixed solution, then transferring the mixed solution into a rotary evaporator, and carrying out rotary evaporation and concentration to 1/3 of the original volume of the mixed solution to obtain a concentrated solution; and (2) immersing the crude modified carrier into the concentrated solution according to the mass ratio of 1:10, putting the crude modified carrier into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment for 30min at the frequency of 50kHz, filtering, separating to obtain impregnated filter residues, putting the impregnated filter residues into a freeze dryer, drying for 2h at the temperature of minus 20 ℃, and discharging to obtain the biomembrane carrier.
Example 2
Weighing 4kg of diatomite, spraying and freezing the diatomite for 2min by using liquid nitrogen, transferring the frozen diatomite into a stone mortar, mashing the diatomite for 1h by using a stone pestle, putting the mashed diatomite into an oven, drying the smashed diatomite at 105 ℃ for 30min, transferring the diatomite into a grinder after drying, continuously grinding the diatomite for 20min, and screening out diatomite particles with the particle size of 1 mm; mixing diatomite particles and a dopamine solution with the mass concentration of 4g/L according to the mass ratio of 1:5 to prepare a mixed solution, adjusting the pH value of the mixed solution to 8.0 by using a sodium hydroxide solution with the concentration of 0.5mol/L, transferring the mixed solution into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment at the frequency of 40kHz for 20min, standing and aging for 1h, and filtering and separating to obtain filter residues; weighing 10g of white phosphorus, igniting the white phosphorus to burn, collecting a burned product, mixing the burned product with absolute ethyl alcohol according to the mass ratio of 1:10, and stirring and mixing the mixture for 2 hours at the rotating speed of 200r/min by using a magnetic stirrer to obtain a reaction solution; weighing 15g of calcium nitrate, dissolving in 150mL of deionized water to obtain a calcium nitrate solution, pouring the filter residue into the calcium nitrate solution according to the mass ratio of 1:5, and dispersing in a high-shear emulsifying and dispersing instrument for 15min to obtain a dispersion liquid; transferring the dispersion liquid into a three-neck flask with a dropping funnel and a stirring device, transferring the three-neck flask into a water bath kettle, raising the temperature of the water bath kettle to 60 ℃, firstly dropwise adding ammonia water with the mass fraction of 25% into the three-neck flask through the dropping funnel, and adjusting the pH value of the dispersion liquid to 9.5; after the pH is adjusted, starting a stirrer to stir at the rotating speed of 200r/min, dripping the reaction liquid into a three-neck flask through a dropping funnel in the stirring process, controlling the dripping speed to be 10mL/min, and after the dripping of the reaction liquid is finished, continuing stirring and reacting for 20 min; after the stirring reaction is finished, transferring the three-neck flask into a sand bath kettle, increasing the sand bath temperature to 170 ℃, standing and aging for 10 hours, filtering, separating to obtain a filter cake, sequentially washing with absolute ethyl alcohol and deionized water for 10 minutes, then putting into an oven, and drying at 105 ℃ for 1 hour to obtain a carrier crude product; weighing 3kg of saponaria mollissima and 1kg of grapes, putting the saponaria mollissima and the grapes into a grinder, grinding for 20min to obtain mixed slurry, mixing the mixed slurry and water according to equal mass ratio, putting the mixture into a fermentation tank, sealing the opening of the fermentation tank, carrying out heat preservation fermentation for 15 days at 22 ℃, and filtering and separating to obtain fermentation liquor after the fermentation is finished; mixing the crude carrier product with fermentation liquor according to the mass ratio of 1:3, placing the mixture in a greenhouse at the temperature of 30 ℃ and the relative air humidity of 60%, naturally standing for 20 hours for reaction, filtering and separating the mixture after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a crude modified carrier product; mixing peach gum, honey, agar and water according to the mass ratio of 20:5:2:40, then putting the mixture into a beaker, then transferring the beaker into an oil bath pot, heating to 80 ℃, stirring and mixing for 10min to obtain a mixed solution, then transferring the mixed solution into a rotary evaporator, and carrying out rotary evaporation and concentration to 1/3 of the original volume of the mixed solution to obtain a concentrated solution; and (2) immersing the crude modified carrier into the concentrated solution according to the mass ratio of 1:10, putting the crude modified carrier into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment for 20min at the frequency of 40kHz, filtering, separating to obtain impregnated filter residues, putting the impregnated filter residues into a freeze dryer, drying for 1h at the temperature of-30 ℃, and discharging to obtain the biomembrane carrier.
Example 3
Weighing 4kg of diatomite, spraying and freezing the diatomite for 2min by using liquid nitrogen, transferring the frozen diatomite into a stone mortar, mashing the frozen diatomite for 1h by using a stone pestle, putting the mashed diatomite into an oven, drying the smashed diatomite at 107 ℃ for 35min, transferring the smashed diatomite into a grinder to continuously grind for 25min after drying is finished, and screening out diatomite particles with the particle size of 2 mm; mixing diatomite particles and a dopamine solution with the mass concentration of 4g/L according to the mass ratio of 1:5 to prepare a mixed solution, adjusting the pH value of the mixed solution to 8.1 by using a sodium hydroxide solution with the concentration of 0.5mol/L, transferring the mixed solution into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment at the frequency of 45kHz for 25min, standing and aging for 2h, and filtering and separating to obtain filter residues; weighing 15g of white phosphorus, igniting the white phosphorus to burn, collecting a burned product, mixing the burned product with absolute ethyl alcohol according to the mass ratio of 1:10, and stirring and mixing the mixture for 3 hours at the rotating speed of 250r/min by using a magnetic stirrer to obtain a reaction solution; weighing 17g of calcium nitrate, dissolving in 170mL of deionized water to obtain a calcium nitrate solution, pouring the filter residue into the calcium nitrate solution according to the mass ratio of 1:5, and placing the calcium nitrate solution into a high-shear emulsifying and dispersing instrument for dispersing for 17min to obtain a dispersion liquid; transferring the dispersion liquid into a three-neck flask with a dropping funnel and a stirring device, transferring the three-neck flask into a water bath kettle, raising the temperature of the water bath kettle to 65 ℃, firstly dropwise adding ammonia water with the mass fraction of 25% into the three-neck flask through the dropping funnel, and adjusting the pH value of the dispersion liquid to 9.7; after the pH is adjusted, starting a stirrer to stir at a rotating speed of 250r/min, dripping the reaction liquid into a three-neck flask through a dropping funnel in the stirring process, controlling the dripping speed to be 12mL/min, and after the dripping of the reaction liquid is finished, continuing stirring and reacting for 25 min; after the stirring reaction is finished, transferring the three-neck flask into a sand bath kettle, increasing the sand bath temperature to 175 ℃, standing and aging for 11h, filtering, separating to obtain a filter cake, sequentially washing with absolute ethyl alcohol and deionized water for 12min, then putting into an oven, and drying at 107 ℃ for 2h to obtain a carrier crude product; weighing 4kg of saponaria mollissima and 1kg of grapes, putting the saponaria mollissima and the grapes into a grinder, grinding for 25min to obtain mixed slurry, mixing the mixed slurry and water according to equal mass ratio, putting the mixture into a fermentation tank, sealing the opening of the fermentation tank, carrying out heat preservation fermentation for 17 days at 23 ℃, and filtering and separating to obtain fermentation liquor after the fermentation is finished; mixing the crude carrier product with fermentation liquor according to the mass ratio of 1:3, placing the mixture in a greenhouse at the temperature of 35 ℃ and the relative air humidity of 65%, naturally standing for reacting for 23 hours, filtering and separating after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a crude modified carrier product; mixing peach gum, honey, agar and water according to the mass ratio of 20:5:2:40, then putting the mixture into a beaker, then transferring the beaker into an oil bath pot, heating to 85 ℃, stirring and mixing for 15min to obtain a mixed solution, then transferring the mixed solution into a rotary evaporator, and carrying out rotary evaporation and concentration to 1/3 of the original volume of the mixed solution to obtain a concentrated solution; and (3) immersing the crude modified carrier into the concentrated solution according to the mass ratio of 1:10, putting the crude modified carrier into an ultrasonic oscillator, carrying out ultrasonic oscillation treatment for 25min at the frequency of 45kHz, filtering, separating to obtain impregnated filter residues, putting the impregnated filter residues into a freeze dryer, drying for 2h at the temperature of minus 25 ℃, and discharging to obtain the biomembrane carrier.
Comparative example: active carbon is used as a biological membrane carrier.
The biofilm carriers of examples 1 to 3 and the control example were subjected to detection, and the detection data are shown in table 1.
TABLE 1
Detecting items Example 1 Example 2 Example 3 Comparative example
Specific surface area (m)2/m3） 5300 5380 5400 780
Saturated Water absorption (1 h, g/g) 8.1 6.9 7.5 Does not absorb water
Amount of biofilm (g/g) 0.89 0.95 0.90 0.41
Biocompatibility Good taste Good taste Good taste Difference (D)
As can be seen from Table 1, the biofilm carrier prepared by the invention has good wetting property, good compatibility with microorganisms and high adsorption capacity.

Claims (7)

1. A preparation method of a biological membrane carrier is characterized by comprising the following specific preparation steps:
(1) spraying and freezing kieselguhr with liquid nitrogen for 2-3 min, mashing the frozen kieselguhr, drying, crushing again, screening out kieselguhr particles with the particle size of 1-3 mm, mixing the kieselguhr particles with a dopamine solution to prepare a mixed solution, adjusting the pH of the mixed solution to 8.0-8.2 with a sodium hydroxide solution, performing ultrasonic oscillation treatment on the mixed solution after the pH is adjusted, standing for aging, and filtering and separating to obtain filter residues for later use;
(2) igniting white phosphorus to burn, collecting a burned product, mixing and stirring the burned product and absolute ethyl alcohol according to a mass ratio of 1:10 for 2-3 hours to obtain a reaction solution for later use;
(3) dissolving calcium nitrate into deionized water according to the mass ratio of 1:10 to obtain a calcium nitrate solution, pouring the filter residue for use in the step (1) into the calcium nitrate solution according to the mass ratio of 1:5, and placing the calcium nitrate solution into a high-shear emulsifying and dispersing instrument for dispersing for 15-20 min to obtain a dispersion liquid;
(4) filling the dispersion into a three-neck flask, transferring the three-neck flask into a water bath kettle, dropwise adding ammonia water with the mass fraction of 25% into the three-neck flask, and adjusting the pH value of the dispersion to 9.5-10.0;
(5) after the pH is adjusted, stirring by using a stirrer, dripping the reaction liquid prepared in the step (2) into a three-neck flask in the stirring process, controlling the dripping speed to be 10-15 mL/min, and after the dripping of the reaction liquid is finished, continuing stirring and reacting for 20-30 min;
(6) after the stirring reaction is finished, transferring the three-neck flask into a sand bath, standing and aging for 10-12 h, filtering, separating to obtain a filter cake, washing for 10-15 min by using absolute ethyl alcohol and deionized water in sequence, and drying to obtain a crude carrier product;
(7) weighing 3-5 kg of saponaria pods and 1-2 kg of grapes, mixing and crushing to obtain mixed slurry, mixing the mixed slurry and water according to an equal mass ratio, loading the mixture into a fermentation tank, carrying out heat preservation fermentation, filtering and separating after the fermentation is finished to obtain fermentation liquor, mixing the carrier crude product and the fermentation liquor, placing the mixture in a greenhouse, naturally standing for reaction, filtering and separating after the reaction is finished to obtain a filter cake, and drying the filter cake to obtain a modified carrier crude product for later use;
(8) mixing peach gum, honey, agar and water, putting the mixture into a beaker, transferring the beaker into an oil bath pot, stirring and mixing to obtain a mixed solution, and concentrating the mixed solution to 1/3 of the volume of the mixed solution to obtain a concentrated solution;
(9) and (4) immersing the crude modified carrier prepared in the step (7) into the concentrated solution, carrying out ultrasonic oscillation treatment, filtering, separating to obtain immersion filter residues, carrying out freeze drying on the immersion filter residues, and discharging to obtain the biomembrane carrier.
2. The method for preparing a biofilm carrier according to claim 1, wherein: the mass ratio of the diatomite particles to the dopamine solution in the step (1) is 1:5, the mass concentration of the dopamine solution is 4g/L, the concentration of the sodium hydroxide solution is 0.5mol/L, the ultrasonic oscillation frequency is 40-50 kHz, the ultrasonic oscillation time is 20-30 min, and the standing and aging time is 1-2 h.
3. The method for preparing a biofilm carrier according to claim 1, wherein: the temperature of the water bath kettle is 60-70 ℃.
4. The method for preparing a biofilm carrier according to claim 1, wherein: the temperature of the sand bath pot is 170-180 ℃.
5. The method for preparing a biofilm carrier according to claim 1, wherein: the heat preservation fermentation temperature in the step (7) is 22-25 ℃, the heat preservation fermentation time is 15-20 days, the mass ratio of the carrier crude product to the fermentation liquid is 1:3, the temperature of a greenhouse is 30-40 ℃, the relative humidity of air is 60-70%, and the standing reaction time is 20-24 hours.
6. The method for preparing a biofilm carrier according to claim 1, wherein: the mass ratio of the peach gum, the honey, the agar and the water in the step (8) is 20:5:2:40, and the temperature of the oil bath pot is 80-90 ℃.
7. The method for preparing a biofilm carrier according to claim 1, wherein: the ultrasonic oscillation frequency in the step (9) is 40-50 kHz, the ultrasonic oscillation time is 20-30 min, the freeze drying temperature is-30 to-20 ℃, and the freeze drying time is 1-2 h.
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